Thioamides and their use as crop protection agents

ABSTRACT

Thioamides of the formula I ##STR1## where A, B, R&#39; are hydrogen, cyano, alkyl, alkoxy or halogen, 
     X is ═CHCH 3  or ═N--OCH 3 , 
     R 1 , R 2  are hydrogen or alky1, 
     Y is a group ##STR2## R is hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl or unsubstituted or substituted hetaryl, 
     and pesticides containing these compounds.

This is a Division of application Ser. No. 08/336,044 filed on Nov. 4,1994, now U.S. Pat. No.5,510,529 which is a Division of application Ser.No. 08/158,390, filed on Nov. 29, 1993, now U.S. Pat. No. 5,393,782.

The present invention relates to novel thioamides, methods of preparingthem, and methods for combatting pests, especially fungi, insects,nematodes and mites, with these compounds.

It is known that certain thiocarbamates (EP 432,503) and certainphenylacetamides (cf. EP 477,631 and 398,692) have a fungicidal orinsecticidal action. However, their action is unsatisfactory.

We have now surprisingly found that novel thioamides of the formula I##STR3## where A, B, R' are identical or different and each is hydrogen,cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halogen,

X is ═CHCH₃ or ═N--OCH₃,

R¹, R² are hydrogen or C₁ -C₄ -alkyl,

Y is a group ##STR4## R is hydrogen, unsubstituted or substituted C₁-C₁₀ -alkyl, unsubstituted or substituted C₁ -C₆ -cycloalkyl,unsubstituted or substituted aryl or unsubstituted or substitutedhetaryl, the term "unsubstituted or substituted" denoting, in additionto hydrogen, halogen, cyano, CO₂ (C₁ -C₄ -alkyl), C(O)(C₁ -C₄ -alkyl),nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄-alkoximino-C₁ -C₄ -alkyl, aryl, aryloxy, benzyloxy, hetaryl, hetaryloxyor C₃ -C₆ -cycloalkyl and the term "hetaryl" denoting an unsubstitutedor substituted aromatic, mono-, di- or trinuclear five-membered orsix-membered heterocycle,

have an excellent fungicidal, insecticidal, nematicidal and acaricidalaction.

The radicals stated in formula I may for example have the followingmeanings:

A, B, R' may be hydrogen, cyano, C₁ -C₄ -alkyl (e.g., methyl), C₁ -C₄-alkoxy (e.g., methoxy) or halogen (fluoro, chloro, bromo, iodo),

X may be ═CHCH₃ or ═N--OCH₃,

R¹, R² may be hydrogen or C₁ -C₄ -alkyl (e.g., methyl, ethyl)

Y is a group ##STR5## R may be hydrogen, unsubstituted or substituted C₁-C₁₀ -alkyl (e.g., methyl, ethyl, n-, isopropyl, n-, iso-, s-, tert.-butyl, trifluoromethyl, cyanomethyl, benzyl, methoxymethyl),unsubstituted or substituted C₁ -C₆ -cycloalkyl (e.g., cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, 1-methylcyclopropyl), unsubstitutedor substituted aryl (e.g., phenyl, 2-methylphenyl, 3-methoxyphenyl,4-tert.-butoxyphenyl, naphthyl, 1-methyl-2-naphthyl), unsubstituted orsubstituted hetaryl (e,g., pyridinyl, 6-Cl-pyridin-2-yl, thiazolyl,2-benzthiazolyl, furyl, 2-furyl, pyrimidinyl, 4-pyrimidinyl), the term"unsubstituted or substituted" denoting, in addition to hydrogen,halogen (e..g, fluoro, chloro, bromo, iodo), cyano, CO₂ (C₁ -C₄ -alkyl)(e.g., CO₂ Me, CO₂ Et), C(O)(C₁ -C₄ -alkyl) (e.g., C(O)CH₃), nitro, C₁-C₄ -alkyl (e.g., methyl, ethyl, n-, isopropyl, n-, i-,s-, tert.-butyl),C₁ -C₄ -alkoxy (e.g., methoxy, ethoxy, n-, isopropoxy, n-, i-, S-,tert.-butoxy), C₁ -C₄ -haloalkyl (e.g., chloromethyl, bromomethyl,trifluoromethyl, 1,1,2,2-tetrafluoroethyl), C₁ -C₄ -alkoximino-C₁ --C₄-alkyl (e.g., methoximinomethyl, ethoximinomethyl, n-,isopropoximinomethyl, n-, i-, s-, tert.-butoximinomethyl,methoximinoethyl), aryl (e.g., phenyl, 1-, 2-naphthyl), aryloxy(phenoxy, 2-naphthyloxy), benzyloxy, hetaryl (e.g., pyridyl,pyrimidinyl, pyridazinyl, quinolinyl, furyl, thienyl, oxazolyl,isoxazolyl, benzthiazolyl, benzthienyl, benzoxazolyl, pyrryl),hetaryloxy (e.g., 2-pyridinyloxy, 2-quinolinyloxy, 4-pyrimidinyloxy), C₃-C₆ -cycloalkyl (e.g., cyclopropyl, cyclobutyl, cyclotDentyl,cyclohexyl) and the term "hetaryl" denoting an unsubstituted orsubstituted aromatic mono-, di- or trinuclear five-membered orsix-membered heterocycle (e.g., pyridine, quinoline, pyrimidine,benzthiazole, benzoxazole).

Preferred compounds of the formula I ##STR6## are those in which A, B,are hydrogen,

X is ═N--OMe,

R¹ is hydrogen,

R² is methyl,

and Y, R' and R have the meanings given in claim 1.

The novel compounds of the formula I may, because of the C═C-- or C═N--double bonds, be obtained as E/Z isomer mixtures. These may be separatedinto their individual components in conventional manner, e.g.,crystallization or chromatography. Both the individual isomericcompounds and mixtures thereof are encompassed by the invention and canbe used as pesticides.

The thioamides of the formula I are prepared for example by reactingamides of the formula II in conventional manner (cf. e.g., Houben-Weyl,vol. IX, pp. 764 et seq.) with a sulfurizing agent such as P₄ S₁₀ orLawesson's reagent ##STR7##

The amides II are known or can be prepared by analogy to known methods(cf. EP 477631, 398692, 463488).

The preparation of the compounds is illustrated by the followingexamples.

EXAMPLE 1 Preparation of2-methoximino-2-[2'-(o-methylphenoxymethyl)-phenyl]aceticacid-N-methylthioamide (compound 2, Table 1).

5 g (16 mmol) of2-methoximino-2-[2'-(o-methylphenoxymethyl)-phenyl]aceticacid-N-methylamide (disclosed in EP 477631) and 8.1 g (20 mmol) ofLawesson's reagent are refluxed for 90 minutes in 50 ml of xylene. Thesolvent is then removed under reduced pressure. The residue waschromatographed twice on silica gel using mixtures of hexane and methyltert-butyl ether, and 1.7 g (32%) of the compound was obtained as ayellow oil.

¹ H-NMR (CDCl₃ /TMS): δ=2.25 (CH₃); 3.21 (d, NHCH₃), 3.95 (OCH₃); 4.97(CH₂); 6.79-7.55 (aryl, 8H); 8.57 (NH).

The compounds listed in the tables below may be obtained analogously:

                                      TABLE 1                                     __________________________________________________________________________     ##STR8##                                                                                                            Phys. data m.p. [°C.]           No.                                                                              Y           R.sup.1                                                                          R.sup.2                                                                          R                 IR [cm.sup.-1 ] H-NMR                  __________________________________________________________________________                                           [ppm]                                  1  CH.sub.2 O  Me H  phenyl                                                   2  CH.sub.2 O  Me H  2-Me-phenyl       3360, 2940, 1595,                                                             1520, 1494, 1241,                                                             1228, 1122, 1052,                                                             1025, 929, 752                         3  CH.sub.2 O  Me H  3-Me-phenyl                                              4  CH.sub.2 O  Me H  4-Me-phenyl                                              5  CH.sub.2 O  Me H  2-Cl-phenyl                                              6  CH.sub.2 O  Me H  3-Cl-phenyl                                              7  CH.sub.2 O  Me H  4-Cl-phenyl                                              8  CH.sub.2 O  Me H  2-F-phenyl                                               9  CH.sub.2 O  Me H  3-F-phenyl                                               10 CH.sub.2 O  Me H  4-F-phenyl                                               11 CH.sub.2 O  Me H  2-Br-phenyl                                              12 CH.sub.2 O  Me H  3-Br-phenyl                                              13 CH.sub.2 O  Me H  4-Br-phenyl                                              14 CH.sub.2 O  Me H  2-OCH.sub.3 -phenyl                                      15 CH.sub.2 O  Me H  3-OCH.sub.3 -phenyl                                      16 CH.sub.2 O  Me H  4-OCH.sub.3 -phenyl                                      17 CH.sub.2 O  Me H  2-CF.sub.3 -phenyl                                       18 CH.sub.2 O  Me H  3-CF.sub.3 -phenyl                                       19 CH.sub.2 O  Me H  4-CF.sub.3 -phenyl                                       20 CH.sub.2 O  Me H  2-CO.sub.2 Me-phenyl                                     21 CH.sub.2 O  Me H  3-CO.sub.2 Me-phenyl                                     22 CH.sub.2 O  Me H  4-CO.sub.2 Me-phenyl                                     23 CH.sub.2 O  Me H  2,3-Me.sub.2 -phenyl                                     24 CH.sub.2 O  Me H  2,4-Me.sub.2 -phenyl                                     25 CH.sub.2 O  Me H  2,5-Me.sub.2 -phenyl                                                                            3360, 2935, 1583,                                                             1519, 1509, 1458,                                                             1358, 1262, 1154,                                                             1130, 1026                             26 CH.sub.2 O  Me H  2,6-Me.sub.2 -phenyl                                     27 CH.sub.2 O  Me H  3,4-Me.sub.2 -phenyl                                     28 CH.sub.2 O  Me H  3,5-Me.sub.2 -phenyl                                     29 CH.sub.2 O  Me H  2,3-Cl.sub.2 -phenyl                                     30 CH.sub.2 O  Me H  2,4-Cl.sub.2 -phenyl                                     31 CH.sub.2 O  Me H  2,5-Cl.sub.2 -phenyl                                     32 CH.sub.2 O  Me H  2,6-Cl.sub.2 -phenyl                                     33 CH.sub.2 O  Me H  3,4-Cl.sub.2 -phenyl                                     34 CH.sub.2 O  Me H  3,5-Cl.sub.2 -phenyl                                     35 CH.sub.2 O  Me H  2-Cl, 4-Me-phenyl                                        36 CH.sub.2 O  Me H  2-Cl, 5-Me-phenyl                                        37 CH.sub.2 O  Me H  2-Me, 4-Cl-phenyl                                        38 CH.sub.2 O  Me H  2-Me, 5-Cl-phenyl                                        39 CH.sub.2 O  Me H  2-pyridyl                                                40 CH.sub.2 O  Me H  3-pyridyl                                                41 CH.sub.2 O  Me H  4-pyridyl                                                42 CH.sub.2 O  Me H  6-Cl-2-pyridyl                                           43 CH.sub.2 O  Me H  6-OCH.sub.3 -2-pyridyl                                   44 CH.sub.2 O  Me H  6-Me-2-pyridyl                                           45 CH.sub.2 O  Me H  5-CF.sub.3 -2-pyridyl                                    46 CH.sub.2 O  Me H  2-quinolyl                                               47 CH.sub.2 O  Me H  3-Me-2-quinolyl                                          48 CH.sub.2 O  Me H  8-Me-2-quinolyl                                          49 CH.sub.2 O  Me H  2-pyrimidinyl                                            50 CH.sub.2 O  Me H  4-CF.sub.3 -2-pyrimidinyl                                51 CH.sub.2 O  Me H  benzothiazol-2-yl                                        52 CH.sub.2 O  Me H  5-Cl-benzothiazol-2-yl                                   53 CH.sub.2 O  Me H  6-Cl-benzothiazol-2-yl                                   54 CH.sub.2 O  Me H  2-Me-4-methoximinomethyl-phenyl                                                                 2.18; 2.27(CH.sub.3);                                                         3.24(d, NHCH.sub.3);                                                          3.96; 3.97(OCH.sub.3);                                                        4.98(CH.sub.2); 6.79-                                                         7.51(Aryl, 7H);                                                               8.61 ppm(NH).                          55 CH.sub.2 O  Me H  2-Me-5-methoximinomethyl-phenyl                          56 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-methoximinomethyl-phenyl                 57 CH.sub.2 O  Me H  2-Me-4-ethoximinomethyl-phenyl                           58 CH.sub.2 O  Me H  2-Me-5-ethoximinomethyl-phenyl                           59 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-ethoximinomethyl-phenyl                  60 CH.sub.2 O  Me H  2-Me-4-n-butoximinomethyl-phenyl                         61 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-n-butoximinomethyl-phenyl                62 CH.sub.2 O  Me H  2-Me-4-allyloximinomethyl-phenyl                         63 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-Allyloximinomethyl-phenyl                64 CH.sub.2 O  Me H  1-naphthyl                                               65 CH.sub.2 O  Me H  2-naphthyl                                               66 CH.sub.2 O  Me H  1-methyl-2-naphthyl                                      67 CH.sub.2 O  Me H  methyl                                                   68 OCH.sub.2   Me H  H                                                        69 OCH.sub.2   Me H  phenyl                                                   70 OCH.sub.2   Me H  2-Cl-phenyl                                              71 OCH.sub.2   Me H  2-Me-phenyl                                              72 CH.sub.2 S  Me H  Me                                                       73 CH.sub.2 S  Me H  phenyl                                                   74 CH.sub.2 S  Me H  2-Me-phenyl                                              75 CH.sub.2 S  Me H  2,5-Cl.sub.2 -phenyl                                     76 CH.sub.2 S  Me H  2-pyridyl                                                77 CH.sub.2 S  Me H  6-Cl-2-pyridyl                                           78 CH.sub.2 S  Me H  benzothiazol-2-yl                                        79 CH.sub.2 S  Me H  5-Cl-benzothiazol-2-yl                                   80 CH.sub.2 S  Me H  6-Cl-benzothiazol-2-yl                                   81 O           Me H  phenyl                                                   82 O           Me H  2-naphthyl                                               83 O           Me H  2-Me-phenyl                                              84 O           Me H  3-Me-phenyl                                              85 O           Me H  4-Me-phenyl                                              86 O           Me H  2-Cl-phenyl                                              87 O           Me H  3-Cl-phenyl                                              88 O           Me H  4-Cl-phenyl                                              89 O           Me H  3-phenoxy-phenyl                                         90 O           Me H  6-(2-CN-phenoxy)-pyrimidin-4-yl                          91 O           Me H  2-pyridyl                                                92 C C         Me H  phenyl                                                   93 C C         Me H  2-Me-phenyl                                              94 C C         Me H  3-Me-phenyl                                              95 C C         Me H  4-Me-phenyl                                              96 C C         Me H  2-Cl-phenyl                                              97 C C         Me H  2,5-Me.sub.2 -phenyl                                     98                                                                                ##STR9##   Me H  phenyl                                                   99                                                                                ##STR10##  Me H  2-Me-phenyl                                              100                                                                               ##STR11##  Me H  3-Me-phenyl                                              101                                                                               ##STR12##  Me H  4-Me-phenyl                                              102                                                                               ##STR13##  Me H  2-Cl-phenyl                                              103                                                                               ##STR14##  Me H  3-Cl-phenyl                                              104                                                                               ##STR15##  Me H  4-Cl-phenyl                                              104                                                                               ##STR16##  Me H  2-F-phenyl                                               105                                                                               ##STR17##  Me H  3-F-phenyl                                               106                                                                               ##STR18##  Me H  4-F-phenyl                                               107                                                                               ##STR19##  Me H  2-Br-phenyl                                              108                                                                               ##STR20##  Me H  3-Br-phenyl                                              109                                                                               ##STR21##  Me H  4-Br-phenyl                                              110                                                                               ##STR22##  Me H  2-CF.sub.3 -phenyl                                       111                                                                               ##STR23##  Me H  3-CF.sub.3 -phenyl                                       112                                                                               ##STR24##  Me H  4-CF.sub.3 -phenyl                                       113                                                                               ##STR25##  Me H  2-OCH.sub.3 -phenyl                                      114                                                                               ##STR26##  Me H  3-OCH.sub.3 -phenyl                                      115                                                                               ##STR27##  Me H  4-OCH.sub.3 -phenyl                                      116                                                                               ##STR28##  Me H  2-CO.sub.2 Me-phenyl                                     117                                                                               ##STR29##  Me H  3-CO.sub.2 Me-phenyl                                     118                                                                               ##STR30##  Me H  4-CO.sub.2 Me-phenyl                                     119                                                                               ##STR31##  Me H  2,3-Me.sub.2 -phenyl                                     120                                                                               ##STR32##  Me H  2,4-Me.sub.2 -phenyl                                     121                                                                               ##STR33##  Me H  2,5-Me.sub.2 -phenyl                                     122                                                                               ##STR34##  Me H  2,6-Me.sub.2 -phenyl                                     123                                                                               ##STR35##  Me H  3,4-Me.sub.2 -phenyl                                     124                                                                               ##STR36##  Me H  3,5-Me.sub.2 -phenyl                                     125                                                                               ##STR37##  Me H  2,3-Cl.sub.2 -phenyl                                     126                                                                               ##STR38##  Me H  2,4-Cl.sub.2 -phenyl                                     127                                                                               ##STR39##  Me H  2,5-Cl.sub.2 -phenyl                                     128                                                                               ##STR40##  Me H  2,6-Cl.sub.2 -phenyl                                     129                                                                               ##STR41##  Me H  3,4-Cl.sub.2 -phenyl                                     130                                                                               ##STR42##  Me H  3,5-Cl.sub.2 -phenyl                                                                            3360, 1583, 1556, 1518, 1409,                                                 1358, 1304, 102, 856, 834, 800                                                cm.sup.-1.                             131                                                                               ##STR43##  Me H  2-Cl, 4-Me-phenyl                                        132                                                                               ##STR44##  Me H  2-Cl, 5-Me-phenyl                                        133                                                                               ##STR45##  Me H  2-Me, 4-Cl-phenyl                                        134                                                                               ##STR46##  Me H  2-Me, 5-Cl-phenyl                                        135                                                                               ##STR47##  Me H  2-pyridyl                                                136                                                                               ##STR48##  Me H  2-naphthyl                                               137                                                                               ##STR49##  Me H  1-Me-2-naphthyl                                          138                                                                               ##STR50##  Me H  2-furyl                                                  139                                                                              CH.sub.2O   Me Me phenyl                                                   140                                                                              CH.sub.2O   Et H  phenyl                                                   141                                                                              CH.sub.2O   Et Et phenyl                                                   __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR51##                                                                                                           Phys. data m.p. [°C.]           No.                                                                              Y           R.sup.1                                                                          R.sup.2                                                                          R                 IR [cm.sup.-1 ] H-NMR                  __________________________________________________________________________                                           [ppm]                                  1  CH.sub.2 O  Me H  phenyl                                                   2  CH.sub.2 O  Me H  2-Me-phenyl                                              3  CH.sub.2 O  Me H  3-Me-phenyl                                              4  CH.sub.2 O  Me H  4-Me-phenyl                                              5  CH.sub.2 O  Me H  2-Cl-phenyl                                              6  CH.sub.2 O  Me H  3-Cl-phenyl                                              7  CH.sub.2 O  Me H  4-Cl-phenyl                                              8  CH.sub.2 O  Me H  2-F-phenyl                                               9  CH.sub.2 O  Me H  3-F-phenyl                                               10 CH.sub.2 O  Me H  4-F-phenyl                                               11 CH.sub.2 O  Me H  2-Br-phenyl                                              12 CH.sub.2 O  Me H  3-Br-phenyl                                              13 CH.sub.2 O  Me H  4-Br-phenyl                                              14 CH.sub.2 O  Me H  2-OCH.sub.3 -phenyl                                      15 CH.sub.2 O  Me H  3-OCH.sub.3 -phenyl                                      16 CH.sub.2 O  Me H  4-OCH.sub.3 -phenyl                                      17 CH.sub.2 O  Me H  2-CF.sub.3 -phenyl                                       18 CH.sub.2 O  Me H  3-CF.sub.3 -phenyl                                       19 CH.sub.2 O  Me H  4-CF.sub.3 -phenyl                                       20 CH.sub.2 O  Me H  2-CO.sub.2 Me-phenyl                                     21 CH.sub.2 O  Me H  3-CO.sub.2 Me-phenyl                                     22 CH.sub.2 O  Me H  4-CO.sub.2 Me-phenyl                                     23 CH.sub.2 O  Me H  2,3-Me.sub.2 -phenyl                                     24 CH.sub.2 O  Me H  2,4-Me.sub.2 -phenyl                                     25 CH.sub.2 O  Me H  2,5-Me.sub.2 -phenyl                                     26 CH.sub.2 O  Me H  2,6-Me.sub.2 -phenyl                                     27 CH.sub.2 O  Me H  3,4-Me.sub.2 -phenyl                                     28 CH.sub.2 O  Me H  3,5-Me.sub.2 -phenyl                                     29 CH.sub.2 O  Me H  2,3-Cl.sub.2 -phenyl                                     30 CH.sub.2 O  Me H  2,4-Cl.sub.2 -phenyl                                     31 CH.sub.2 O  Me H  2,5-Cl.sub.2 -phenyl                                     32 CH.sub.2 O  Me H  2,6-Cl.sub.2 -phenyl                                     33 CH.sub.2 O  Me H  3,4-Cl.sub.2 -phenyl                                     34 CH.sub.2 O  Me H  3,5-Cl.sub.2 -phenyl                                     35 CH.sub.2 O  Me H  2-Cl-, 4-Me-phenyl                                       36 CH.sub.2 O  Me H  2-Cl-, 5-Me-phenyl                                       37 CH.sub.2 O  Me H  2-Me-, 4-Cl-phenyl                                       38 CH.sub.2 O  Me H  2-Me-, 5-Cl-phenyl                                       39 CH.sub.2 O  Me H  2-pyridyl                                                40 CH.sub.2 O  Me H  3-pyridyl                                                41 CH.sub.2 O  Me H  4-pyridyl                                                42 CH.sub.2 O  Me H  6-Cl-2-pyridyl                                           43 CH.sub.2 O  Me H  6-OCH.sub.3 -2-pyridyl                                   44 CH.sub.2 O  Me H  6-Me-2-pyridyl                                           45 CH.sub.2 O  Me H  5-CF.sub.3 -2-pyridyl                                    46 CH.sub.2 O  Me H  2-quinolyl                                               47 CH.sub.2 O  Me H  3-Me-2-quinolyl                                          48 CH.sub.2 O  Me H  8-Me-2-quinolyl                                          49 CH.sub.2 O  Me H  2-pyrimidinyl                                            50 CH.sub.2 O  Me H  4-CF.sub.3 -2-pyrimidinyl                                51 CH.sub.2 O  Me H  benzothiazol-2-yl                                        52 CH.sub.2 O  Me H  5-Cl-benzothiazol-2-yl                                   53 CH.sub.2 O  Me H  6-Cl-benzothiazol-2-yl                                   54 CH.sub.2 O  Me H  2-Me-4-methoximinomethyl-phenyl                          55 CH.sub.2 O  Me H  2-Me-5-methoximinomethyl-phenyl                          56 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-methoximinomethyl-phenyl                 57 CH.sub.2 O  Me H  2-Me-4-ethoximinomethyl-phenyl                           58 CH.sub.2 O  Me H  2-Me-5-ethoximinomethyl-phenyl                           59 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-ethoximinomethyl-phenyl                  60 CH.sub.2 O  Me H  2-Me-4-n-butoximinomethyl-phenyl                         61 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-n-butoximinomethyl-phenyl                62 CH.sub.2 O  Me H  2-Me-4-allyloximinomethyl-phenyl                         63 CH.sub.2 O  Me H  2,5-Me.sub.2 -4-allyloximinomethyl-phenyl                64 CH.sub.2 O  Me H  1-naphthyl                                               65 CH.sub.2 O  Me H  2-naphthyl                                               66 CH.sub.2 O  Me H  1-methyl-2-naphthyl                                      67 CH.sub.2 O  Me H  methyl                                                   68 OCH.sub.2   Me H  H                                                        69 OCH.sub.2   Me H  phenyl                                                   70 OCH.sub.2   Me H  2-Cl-phenyl                                              71 OCH.sub.2   Me H  2-Me-phenyl                                              72 CH.sub.2 S  Me H  Me                                                       73 CH.sub.2 S  Me H  phenyl                                                   74 CH.sub.2 S  Me H  2-Me-phenyl                                              75 CH.sub.2 S  Me H  2,5-Cl.sub.2 -phenyl                                     76 CH.sub.2 S  Me H  2-pyridyl                                                77 CH.sub.2 S  Me H  6-Cl-2-pyridyl                                           78 CH.sub.2 S  Me H  benzothiazol-2-yl                                        79 CH.sub.2 S  Me H  5-Cl-benzothiazol-2-yl                                   80 CH.sub.2 S  Me H  6-Cl-benzothiazol-2-yl                                   81 O           Me H  phenyl                                                   82 O           Me H  2-naphthyl                                               83 O           Me H  2-Me-phenyl                                              84 O           Me H  3-Me-phenyl                                              85 O           Me H  4-Me-phenyl                                              86 O           Me H  2-Cl-phenyl                                              87 O           Me H  3-Cl-phenyl                                              88 O           Me H  4-Cl-phenyl                                              89 O           Me H  3-phenoxy-phenyl                                         90 O           Me H  6-(2-CN-phenoxy)-pyrimidin-4-yl                          91 O           Me H  2-pyridyl                                                92 CC          Me H  phenyl                                                   93 CC          Me H  2-Me-phenyl                                              94 CC          Me H  3-Me-phenyl                                              95 CC          Me H  4-Me-phenyl                                              96 CC          Me H  2-Cl-phenyl                                              97 CC          Me H  2,5-Me.sub.2 -phenyl                                     98                                                                                ##STR52##  Me H  phenyl                                                   99                                                                                ##STR53##  Me H  2-Me-phenyl                                              100                                                                               ##STR54##  Me H  3-Me-phenyl                                              101                                                                               ##STR55##  Me H  4-Me-phenyl                                              102                                                                               ##STR56##  Me H  2-Cl-phenyl                                              103                                                                               ##STR57##  Me H  3-Cl-phenyl                                              104                                                                               ##STR58##  Me H  4-Cl-phenyl                                              104                                                                               ##STR59##  Me H  2-F-phenyl                                               105                                                                               ##STR60##  Me H  3-F-phenyl                                               106                                                                               ##STR61##  Me H  4-F-phenyl                                               107                                                                               ##STR62##  Me H  2-Br-phenyl                                              108                                                                               ##STR63##  Me H  3-Br-phenyl                                              109                                                                               ##STR64##  Me H  4-Br-phenyl                                              110                                                                               ##STR65##  Me H  2-CF.sub.3 -phenyl                                       111                                                                               ##STR66##  Me H  3-CF.sub.3 -phenyl                                       112                                                                               ##STR67##  Me H  4-CF.sub.3 -phenyl                                       113                                                                               ##STR68##  Me H  2-OCH.sub.3 -phenyl                                      114                                                                               ##STR69##  Me H  3-OCH.sub.3 -phenyl                                      115                                                                               ##STR70##  Me H  4-OCH.sub.3 -phenyl                                      116                                                                               ##STR71##  Me H  2-CO.sub.2 Me-phenyl                                     117                                                                               ##STR72##  Me H  3-CO.sub.2 Me-phenyl                                     118                                                                               ##STR73##  Me H  4-CO.sub.2 Me-phenyl                                     119                                                                               ##STR74##  Me H  2,3-Me.sub.2 -phenyl                                     120                                                                               ##STR75##  Me H  2,4-Me.sub.2 -phenyl                                     121                                                                               ##STR76##  Me H  2,5-Me.sub.2 -phenyl                                     122                                                                               ##STR77##  Me H  2,6-Me.sub.2 -phenyl                                     123                                                                               ##STR78##  Me H  3,4-Me.sub.2 -phenyl                                     124                                                                               ##STR79##  Me H  3,5-Me.sub.2 -phenyl                                     125                                                                               ##STR80##  Me H  2,3-Cl.sub.2 -phenyl                                     126                                                                               ##STR81##  Me H  2,4-Cl.sub.2 -phenyl                                     127                                                                               ##STR82##  Me H  2,5-Cl.sub.2 -phenyl                                     128                                                                               ##STR83##  Me H  2,6-Cl.sub.2 -phenyl                                     129                                                                               ##STR84##  Me H  3,4-Cl.sub.2 -phenyl                                     130                                                                               ##STR85##  Me H  3,5-Cl.sub.2 -phenyl                                     131                                                                               ##STR86##  Me H  2-Cl-, 4-Me-phenyl                                       132                                                                               ##STR87##  Me H  2-Cl-, 5-Me-phenyl                                       133                                                                               ##STR88##  Me H  2-Me-, 4-Cl-phenyl                                       134                                                                               ##STR89##  Me H  2-Me-, 5-Cl-phenyl                                       135                                                                               ##STR90##  Me H  2-pyridyl                                                136                                                                               ##STR91##  Me H  2-naphthyl                                               137                                                                               ##STR92##  Me H  1-Me-2-naphthyl                                          138                                                                               ##STR93##  Me H  2-furyl                                                  139                                                                              CH.sub.2 O  Me Me phenyl                                                   140                                                                              CH.sub.2 O  Et H  phenyl                                                   141                                                                              CH.sub.2 O  Et Et phenyl                                                   __________________________________________________________________________

The novel compounds are suitable as fungicides, insecticides andnematocides.

The active ingredients according to the invention, or agents containingthem, may be applied for instance in the form of directly sprayablesolutions, powders, suspensions (including high-percentage aqueous, oilyor other suspensions), dispersions, emulsions, oil dispersions, pastes,dusts, broadcasting agents, or granules by spraying, atomizing, dusting,broadcasting or watering. The forms of application depend entirely onthe purpose for which the agents are being used, but they must ensure asfine a distribution of the active ingredients according to the inventionas possible.

Normally, the plants are sprayed or dusted with the active ingedients orthe seeds of the plants are treated with the active ingredients.

The formulations are produced in known manner, for example by extendingthe active ingredient with solvents and/or carriers, with or without theuse of emulsifiers and dispersants; if water is used as solvent, it isalso possible to employ other organic solvents as auxiliary solvents.Suitable auxiliaries for this purpose are solvents such as aromatics(e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins(e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones(e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide),and water; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin-sulfitewaste liquors and methylcellulose.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid,phenolsulfonic acid, naphthalenesulfonic acid anddibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, andsalts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof fatty alcohol glycol ethers, condensation products of sulfonatednaphthalene and naphthalene derivatives with formaldehyde, condensationproducts of naphthalene or naphthalenesulfonic acids with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acids, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain meals, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

Examples of such formulations are given below.

I. A solution of 90 parts by weight of compound 2 from Table 1 and 10parts by weight of N-methyl-α-pyrrolidone, which is suitable forapplication in the form of very fine drops.

II. A mixture of 20 parts by weight of compound 25 from Table 1, 80parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 moleof castor oil. By finely dispersing the mixture in water, a dispersionis obtained.

III. An aqueous dispersion of 20 parts by weight of compound 54 fromTable 1, 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil.

IV. An aqueous dispersion of 20 parts by weight of compound 130 fromTable 1, 25 parts by weight of cyclohexanol, 65 parts by weight of amineral oil fraction having a boiling point between 210 and 280° C, and10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil.

V. A hammer-milled mixture of 80 parts by weight of compound 2 fromTable 1, 3 parts by weight of the sodium salt ofdiisobutyl-naphthalene-α-sulfonic acid, 10 parts by weight of the sodiumsalt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and7 parts by weight of powdered silica gel. By finely dispersing themixture in water, a spray liquor is obtained.

VI. An intimate mixture of 3 parts by weight of compound 25 from Table 1and 97 parts by weight of particulate kaolin. The dust contains 3 wt% ofthe active ingredient.

VII. An intimate mixture of 30 parts by weight of compound 54 from Table1, 92 parts by weight of powdered silica gel and 8 parts by weight ofparaffin oil sprayed onto the surface of this silica gel. Thisformulation of the active ingredient exhibits good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound 130from Table 1, 10 parts of the sodium salt of a phenolsulfonicacid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts ofwater, which dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of compound 2 fromTable 1, 2 parts by weight of the calcium salt of dodecylbenzenesulfonicacid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts byweight of the sodium salt of a phenolsulfonic acid-urea-formaldehydecondensate and 68 parts by weight of a paraffinic mineral oil.

The novel compounds are extremely effective on a broad spectrum ofphytopathogenic fungi, in particular those from the class consisting ofthe Ascomycetes and Basidiomycetes. Some of them have systemic mobilityand action after application to the soil and foliage.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially-wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, grapevines, fruit and ornamentals, and in vegetables such ascucumbers, beans and cucurbits.

The compounds are applied by treating the seeds, plants, materials orsoil to be protected against fungus attack with a fungicidally effectiveamount of the active ingredients. The compounds may be applied before orafter infection of the materials, plants or seeds by the fungi.

The compounds I are particularly useful for controlling the followingplant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia solani in cotton,

Ustilago species in cereals and sugar cane,

venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables.

The novel compounds may also be used for protecting materials (timber),for example against Paecilomyces variotii.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt% of active ingredient.

The application rates depend on the type of effect desired, but aregenerally from 0.02 to 3 kg of active ingredient per hectare.

When the active ingredients are used for treating seed, applicationrates of from 0.001 to 50, and preferably from 0.01 to 10, g per kg ofseed are generally required.

When the agents according to the invention are used as fungicides, theymay be employed together with other active ingredients, e.g.,herbicides, insecticides, growth regulators, other fungicides andfertilizers.

USE EXAMPLE 1 Action on Plasmopara viticola

Leaves of potted vines of the M uller-Thurgau variety were sprayed withaqueous suspensions containing (dry basis) 80% of active ingredient and20% of emulsifier. To assess the duration of action, the plants were setup, after the sprayed-on layer had dried, for 8 days in the greenhouse.Then the leaves were infected with a zoospore suspension of Plasmoparaviticola. The plants were first placed for 48 hours in a watervapor-saturated chamber at 24° C and then in a greenhouse for 5 days atfrom 20 to 30 ° C. To accelerate and intensify the sporangiophoredischarge, the plants were then again placed in the moist chamber for 16hours. The extent of fungus attack was then assessed on the undersidesof the leaves.

The results of the experiment show that compounds nos. 2, 25 and 54 fromTable I, when applied as spray liquors containing 63 ppm of activeingredient, have a very good fungicidal action (0% attack).

USE EXAMPLE 2 Action on Botrytis cinerea in paprika

Slices of green paprika pods were sprayed to runoff with aqueousformulations containing (dry basis) 80% of active ingredient and 20% ofemulsifier. Two hours after the sprayed-on layer had dried, the sliceswere inoculated with a spore suspension of Botrytis cinerea whichcontained 1.7×10⁶ spores per ml of a 2% strength biomalt solution. Theinoculated slices were then incubated for 4 days in moist chambers.Botrytis spread on the slices was then assessed visually.

The results show that compounds nos. 2, 25 and 54 from Table I, whenapplied as spray liquors containing 500 ppm of active ingredient, have avery good fungicidal action (5% attack).

We claim:
 1. A thioamide of the formula I, ##STR94## where A, B, and R'are identical or different and each is hydrogen, cyano, C₁₋₄ -alkyl,C₁₋₄ -alkoxy or halogen;X is ═CHCH₃ OR ═N--OCH_(3;) R¹ and R² arehydrogen or C₁₋₄ -alkyl; Y is --CH₂ --O--N═C(R')--; and R is hydrogenunsubstituted or substituted C₁₋₁₀ -alkyl, unsubstituted or substitutedC₁₋₆ cycloalkyl, unsubstituted or substituted aryl the term"unsubstituted or substituted" denoting, in addition to hydrogen,halogen, cyano C(O) (C₁ -C₄ -alkyl) , nitro, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoximino-C₁ -C₄ -alkyl, aryl,aryloxy, benzyloxy or C₃ -C₆ -cycloalkyl.
 2. A composition comprising aninert carrier and a fungicidally or pesticidally effective amount of athioamide derivative of the formula (I), ##STR95## where A, B, and R'are identical or different and each is hydrogen, cyano, C₁₋₄ -alkyl,C₁₋₄ -alkoxy or halogen;X is ═CHCH₃ OR ═N--OCH_(3;) R¹ and R² arehydrogen or C₁₋₄ -alkyl; Y is --CH₂ --O--N═C(R')--; and R is hydrogenunsubstituted or substituted C₁₋₁₀ -alkyl, unsubstituted or substitutedC₁₋₆ cycloalkyl, unsubstituted or substituted aryl the term"unsubstituted or substituted" denoting, in addition to hydrogen,halogen, cyano, C(O) (C₁ -C₄ -alkyl), nitro, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoximino-C₁ -C₄ -alkyl, aryl,aryloxy, benzyloxy or C₃ -C₆ -cycloalkyl.
 3. A method of combattingfungi, comprising applying onto a material, plant, seed or soil in needthereof a fungicidally effective amount of a thioamide derivative of theformula (I), ##STR96## where A, B, and R' are identical or different andeach is hydrogen, cyano, C₁₋₄ -alkyl, C₁₋₄ -alkoxy or halogen;X is═CHCH₃ OR ═N--OCH₃ ; R¹ and R² are hydrogen or C₁₋₄ -alkyl; Y is --CH₂--O--N═C(R')--; and R is hydrogen unsubstituted or substituted C₁₋₁₀-alkyl, unsubstituted or substituted C₁₋₆ cycloalkyl, unsubstituted orsubstituted aryl the term "unsubstituted or substituted" denoting, inaddition to hydrogen, halogen, cyano C(O) (C₁ -C₄ -alkyl), nitro, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkximino-C₁ -C₄-alkyl, aryl, aryloxy, benzyloxy, or C₃ -C₆ -cycloalkyl.
 4. Thioamidederivatives of the formula I as claimed in claim 1, where X is ═CHCH₃,R¹ is hydrogen and R² is methyl, A and B are hydrogen and Y and R havethe meanings given in claim
 1. 5. Thioamide derivatives of the formula Ias claimed in claim 1, where X is ═N--OCH₃, R¹ is hydrogen and R² ismethyl, A and B are hydrogen and Y and R have the meanings given inclaim 1.